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Other Emerging Bioplastics Dawn A. Smith, Scion
Emerging bioplastics
• Bio-refinery concept • Recent advances in renewable resourced
traditional plastics − Bio-polyethylene (bio-PP & bio-PVC proposed) − Hybrids − Bio-PET − Bio-polyamides and polyurethanes − Bio-blends
• Latest advances in additive technologies for bioplastics
Moving to renewably resourced plastics
Heat, pressure
Millions of years
Modern chemical
processes
Plastics PE, PP PET, …
bio-Plastics bio-PE, bio-PP bio-PET, …
Supplementing Supply Chain
• Price of crude oil fluctuates, so price of intermediates and polymers fluctuates.
• Industrial biotechnology − True drop-in materials (origin only
difference) − Supplement the existing supply chain − Lower price volatility
• Agriculture can also be volatile. • Future feedstock: biomass / municipal
waste • “story” or not, it’s good business
Oil-Refineries and Bio-Refineries • Oil-refinery:
− Crude oil (finite) as feedstock − Established technology − Very efficient use of feedstock
• Bio-refinery (1st generation)
− Starch/sugar (renewable) as feedstock − Technology established − Efficient use of feedstock
• Bio-refinery (2nd generation)
− Non-food biomass (renewable) as feedstock − Logistics? − Technology under development
Bio-ethylene • No technical hurdles for producing ethylene from
sugars/starch
• Braskem (Brazil) − Q4 2010: 250,000 tpa − Planned by Q4 2012: 1 million tpa
• Dow/Mitsui (Brazil) − Planned by 2015: 350,000 tpa bioethanol
• Solvay (Brazil) − Planned PVC and PVA from bioethylene − expected capacity of 60,000 tpa of bioethylene for
conversion into PVC.
renewable; not compostable
PE: polyethylene ethylene
bioethanol
Brazil - Braskem • 80% of the plant’s production already sold
− Toyota, Tetrapak, P&G …… − blown packaging (food & hygiene products) − household appliances, toy & automobile industries
• Bio-HDPE potential for lower cost than petrochemical
technology − initial pricing ~ 25-50% higher
• Bio-based butene bio-derived LLDPE
• Bio-polypropylene - under development
Bio-ethylene glycol from bio-ethanol
• Bio-ethylene glycol (bio-EG) − India Glycols - from bio-ethanol since 1989
− Novepha in China
− GTC (Greencol Taiwan Corp), a 50/50 JV (China Man-Made Fiber & Toyota Tsusho ), is building a 100,000 metric ton biobased ethylene facility in Taiwan and will produce bio-EG
H2C=CH2 H2C CH2
OH
OH
ethylene ethylene glycol
Hybrid Polyester - PET • “Partial Bio-PET” The PlantBottleTM
− bio-EG (the ”E” in PET) → ~30% renewable − sugar cane / molasses (Brazil) to bioethanol to bio-EG − future feedstocks: corn stover, switchgrass, wood chips − Terephthalic acid = non-renewable content − processes in existing manufacturing/recycling facilities
Bottle-Wars ! • Pepsi unveils 100% plant based PET bottle (2011)
• PepsiCo. has developed its own bio-PET bottle – 100% bio-based raw
materials • The bio-PET is manufactured using the company's agricultural by-products
from its food business, including switch grass, pine bark and corn husks.
• Processes in existing manufacturing/recycling facilities
• Pilot production phase of bottle in 2012
Bio-paraxylene (PX)
• US-based Virent to produce bio-PX in a commercial biorefinery via catalytic chemical reactions (not fermentation) from plant sugars
• PX is a precursor for terephthalic acid, PET
• In 2011 - 38,000 L PX / year
p-xylene terephthalic acid
More bio-intermediates • Bio-succinic acid
− BioAmber, DSM/Roquette, BASF/Purac, Mitsubishi and Myriant
• Bio-butanediol (also THF and γ-butyrolactone) − Tate & Lyle, M & G and Mitsubishi Chemical
• Bio-isobutene and isobutanol − Gevo/Cargill and LANXESS
• Bio-acrylic acid − Dow, Arkema, BASF and Nippon Shokubai
• Bio-methyl methacrylate − Arkema and Evonik
Bio-polyamides (Nylons) based castor oil Nylon11 (100% castor oil) • Arkema/Atofina: Rilsan • Rhodia: Technyl
Nylon4,10; Nylon6,10 (~60 – 70%) • BASF: Ultramid Balance • DSM: EcoPaXX • DuPont: Zytel • Evonik: Vestamid Terra HS
Nylon10,10 (100%) • DuPont: Zytel • Evonik: Vestamid Terra DS
bio-based TPE from Nylon11 / polyether blocks − Arkema Pebax® Rnew
“The big reason for the surge in castor oil nylons is reduction of the material's carbon footprint “
Mazda car panels
Bio-polyurethanes • Bio-polyurethanes / bio–polyols (soy or castor oil)
Bayer, Huntsman, Urethane Soy Systems Co. (USSC) Dow RENUVA™ Technology (soy) Agrol® polyols (soy) Vertellus (castor)
• Mouldings & Foams • Lupranol Balance 50 foams (BASF)
Bio-polyols Produce less emissions, use less total energy
•Note: isocyanate component still petrochemical based
Ford Motor Company – now (and then) • As of 2011, all Ford North American-built vehicles
use bio-based foam in seat cushions and backs.
• Henry Ford unveiled the now-legendary "soybean car," with soy-based plastic body panels, in 1941.
media.ford.com
NEW intermediates
• Industrial biotechnology is a way to supplement existing supply chains
• Not seen as a source of novel green intermediates YET!
• Current materials don’t meet all needs.
New monomers – FDCA by Avantium • FDCA from fructose, similar to terephthalate (PET)
− Pilot plant - 40 tpa of FDCA monomer in 2H 2011 − Polymerise with EG to for PEF − Solvay and Avantium to jointly develop green
engineering plastics - polyamides from FDCA
FDCA Terephthalic acid
New polymers – PEF “yxy” by Avantium • PEF “yxy” – a PET alternative
− 6 x O2 barrier than PET − 2 x CO2 & H2O barrier than PET − Higher Tg and lower processing temp than PET
FDCA
+
bio EG
renewable; not compostable
Bioplastic Blends
Hybrid Blends • Biopolymers
− relatively costly − less than desired properties or processability
• Blends (PVC-PLA, PC-PLA, PET-PLA …)
− Can claim x% renewable content − retain properties and reduce cost
• Natureworks PLA 3801X: 80% biobased (PLA)
− thermal stability to 120ºC & high impact strength • PolyOne - reSound Biopolymer: ≥ 30% PLA, PHB, or PHBV • RTP Company
− PLA - Bio-PA blends: 32-80% bio-content − PLA with PC, PMMA, or ABS
• Starch blends
− Starch-PE; Starch–PP etc (Cereplast & others…..) Caution “biopropylene”
PLA Blends: “Bio-Polycarbonate” • Bayer Material Science
− two bio-content PC/PLA blends • Unitika : hybrid PLA,PC, compatibiliser
− increased HDT, reduced brittleness and rapid crystallisation − suitable for electronics applications
• Mitsubishi Plastics
• PLA/PC blends don’t readily decompose like PLA • Uses include mobile/smart phones, portable electronics, furniture,
sporting goods and automotive interiors
• In some examples, PLA improves the properties − Samsung Reclaim uses PLA/PC for cell phone housing − PC/PLA showed better fatigue resistance than PC/ABS
www.samsung.com
PLA - Blends • ABS with PLA, a 2-phase blend that is opaque with reduced
brittleness
• Blending PLA with PE or copolyesters also reduces brittleness − e.g. FKuR Bio-flex – PLA with copolyesters
• Unitika − PLA/PMMA blends (clear): PMMA raises Tg − developing PLA alloys with PP and PC
• Polymaterial Technology Co. (Thailand) − Four commercial EcoHybrid grades are alloys of bio- and petro-based
plastics: PLA/PHA with either PP, TPU, PETG or ABS − Heat-resistant PLA/PHA and PLA/PHBV compounds with Tg up to
80 C for injection moulded durables - dishes and housewares
• PLA/Nylon 6 compounds for durable applications
Fully degradable toothpaste tube for Swedish company, FKuR Bioresin
Trends in Additive Technologies
Additive Technologies
• Plastics Additives industry • Additives for bioplastics to improve/change
properties • Bio-fillers for all plastics
Plastic Additives • >US$30B • plasticisers, colourants • impact modifiers, flame retardants • heat/light stabilisers, • antioxidants, antimicrobials • conductive: heat/thermal • anti-fogging; lubricants/release..
• Major producers
− Chemtura, Exxon Mobil − BASF-Ciba, Eastman, − Rohm & Haas (Dow), − Ferro, Arkema, Akzo Nobel, − Clariant, Albermarle
• PVC major market
Additives for Bioplastics
• Sukano • Danimer • DuPont • Rohm & Haas (Dow) • Arkema • Polyone
• Clariant • Ampacet • Teknor • Cereplast • BASF
Various companies are investing in additives and compounds for bioplastics:
Additives for Bioplastics • Not all options are bio-based
• “Traditional” additives
− no adverse effects (health, environment; compostability stds) • “Renewable" additives derived from natural sources
− not necessarily biodegradable: renewable story/benefits • “Renewable” and “biodegradable”
− single-use/short-lived products or end-of-life compostability
• Tianan Biologic (PHBV)
− “not bound by renewably sourced additives, as long as no adverse effects”
• Metabolix, and Meredian (PHAs) − “only biobased additives”
Impact/Strength Modifiers for PLA
− Biostrength® 280 Impact Modifier for PLA clear − Biostrength® 150 Impact Modifier for PLA opaque − Teknor Apex will supply masterbatches based on these
additives under its Terraloy™ bioplastics brand name.
− Paraloid ™ BPM-500 and 515 Acrylic Impact Modifiers for PLA clear
− Paraloid ™ BPM-520 Impact Modifier for PLA opaque
− Biomax® Strong additives for impact strength, flexibility and melt stability for PLA clear
Sukano im S555 – impact modifier for PLA clear Danimer Impact Modifier
HDT additive – raises HDT from ~57 C for neat PLA to
as high as 100 C
Danimer HDT modifier to 88 C
Biomax Thermal 300 modifier to 95 C Terraloy BP-39070 series to 100 C (high heat & impact
resistant - microwaveable, thermoformed trays)
Biostrength® 900 Metal Release for PLA
Sukano mr S533 – mold release
Heat Deflection Temperature (HDT) enhancers
Mould release agents
Melt strength modifiers Biostrength® 700 Melt Strength Enhancer
Joncryl® ADR Chain Extender for PLA
Clariant’s CESA-extend chain extender
Colour/Opacity/Clarity modifiers translucent & opaque masterbatches Renol-natur color masterbatches -“all-natural” pigments
derived from plants. Sukano na S516 and na S516-IceClear – transparent
and opaque nucleating agents Sukano ob S515-N or ob S515-BL – optical brightener and white, black, and colour masterbatches PolyOne Bio-Color (partly sustainable raw materials) Teknor Color for PLA resins and blends.
UV resistance / antioxidants
CESA-natur antioxidants, which use natural
antioxidants like vitamin E
Sukano dc S511 – anti-blocking Sukano as S546 – antistatic CESA-natur antistatic masterbatches
Others
Plasticisers – natural alternatives • Alternates to phthalate plasticisers for PVC
− Polyone and ADM – soybean-based − Segetis – ketal monomers from corn cobs − Roquette - Polysorb ID37 from isosorbides − Dow ECOLIBRIUM™ Bio-Based Plasticizers
Specifically for wire and cable applications
• General Bio-based Plasticisers
− Glycerols/polyglycerol/glycerides − Sorbitols, lactates, citrates
“open source” strategy - Ingeo™ 3801X • Ingeo 3801X – semi-durable, not certified as compostable, high-
heat, high-impact bioresin
• Spurring innovation, NatureWorks LLC provides open source access to both formulation and compounding procedure.
• The full details of Ingeo 3801X recipe including impact modifier, crystallisation accelerant, and agents for reinforcement and nucleation are openly available to Ingeo customers.
Bio-fillers for all plastics – “weight savers” • LignoMAXX – steam-exploded DDGs (Lignotech) • Agriplast – wheat straw reinforced compounds • Scion WPP – recently licensed to Sonae Industria • Kareline® composites - fibre reinforced
thermoplastic composites in PP, ABS, PS, acetal and PLA
• Fibrolon (FKuR) – injection mouldable − Fibrolon P = PP with ~40% wood fibre − Fibrolon F = PLA with wood fibre
• Neroplast – xylite from lignite coal − Hydrophobic filler that can be processed with Nylon – up to
280C
The Future For Bio-Additives • More & More “Bio-based”
− Gas barrier enhancements − Tough (& transparent) − Heat & fire resistance − Durability − Anti-microbial − Anti-oxidant / stabilisers
Scion has technologies and current programmes in all of these ….most using NZ resources or residues www.scionresearch.com